US4276089A - Anticorrosion composition - Google Patents
Anticorrosion composition Download PDFInfo
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- US4276089A US4276089A US06/083,553 US8355379A US4276089A US 4276089 A US4276089 A US 4276089A US 8355379 A US8355379 A US 8355379A US 4276089 A US4276089 A US 4276089A
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- corrosion
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- 239000000203 mixture Substances 0.000 title claims abstract description 61
- 238000005260 corrosion Methods 0.000 claims abstract description 88
- 239000002253 acid Substances 0.000 claims abstract description 73
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229920000768 polyamine Polymers 0.000 claims abstract description 36
- 150000007513 acids Chemical class 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 7
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 5
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 3
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 21
- 125000002947 alkylene group Chemical group 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 6
- 125000005907 alkyl ester group Chemical group 0.000 claims description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- SUYARWBGPSQLRC-UHFFFAOYSA-N [bis(2-hydroxyethyl)amino]methylphosphonic acid Chemical compound OCCN(CCO)CP(O)(O)=O SUYARWBGPSQLRC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims 1
- 239000000725 suspension Substances 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 48
- 239000007788 liquid Substances 0.000 abstract description 5
- 238000012360 testing method Methods 0.000 description 41
- 238000005259 measurement Methods 0.000 description 26
- 150000001412 amines Chemical class 0.000 description 19
- 229910052802 copper Inorganic materials 0.000 description 19
- 239000010949 copper Substances 0.000 description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 18
- 229910000831 Steel Inorganic materials 0.000 description 18
- 239000010959 steel Substances 0.000 description 18
- 239000004411 aluminium Substances 0.000 description 16
- 229910052782 aluminium Inorganic materials 0.000 description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 16
- 239000003112 inhibitor Substances 0.000 description 16
- 150000003839 salts Chemical class 0.000 description 16
- 235000020679 tap water Nutrition 0.000 description 15
- 239000008399 tap water Substances 0.000 description 13
- 208000016261 weight loss Diseases 0.000 description 13
- 230000004580 weight loss Effects 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 150000002739 metals Chemical class 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 239000006072 paste Substances 0.000 description 9
- 239000000523 sample Substances 0.000 description 9
- 239000008234 soft water Substances 0.000 description 9
- 239000003643 water by type Substances 0.000 description 9
- 239000011521 glass Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 101100204264 Arabidopsis thaliana STR4 gene Proteins 0.000 description 6
- 101150076149 TROL gene Proteins 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 6
- 239000011707 mineral Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- DKPHLYCEFBDQKM-UHFFFAOYSA-H hexapotassium;1-phosphonato-n,n-bis(phosphonatomethyl)methanamine Chemical compound [K+].[K+].[K+].[K+].[K+].[K+].[O-]P([O-])(=O)CN(CP([O-])([O-])=O)CP([O-])([O-])=O DKPHLYCEFBDQKM-UHFFFAOYSA-H 0.000 description 5
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical class NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- -1 thiazols Chemical class 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 238000009434 installation Methods 0.000 description 4
- 150000003973 alkyl amines Chemical class 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000003359 percent control normalization Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 150000003009 phosphonic acids Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 101150108015 STR6 gene Proteins 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- JVVXZOOGOGPDRZ-SLFFLAALSA-N [(1R,4aS,10aR)-1,4a-dimethyl-7-propan-2-yl-2,3,4,9,10,10a-hexahydrophenanthren-1-yl]methanamine Chemical compound NC[C@]1(C)CCC[C@]2(C)C3=CC=C(C(C)C)C=C3CC[C@H]21 JVVXZOOGOGPDRZ-SLFFLAALSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- IPZJQDSFZGZEOY-UHFFFAOYSA-N dimethylmethylene Chemical compound C[C]C IPZJQDSFZGZEOY-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical class [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 208000020442 loss of weight Diseases 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000001457 metallic cations Chemical class 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003007 phosphonic acid derivatives Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- 101150117395 str4 gene Proteins 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 230000003442 weekly effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
Definitions
- the present invention relates to an anti-corrosion composition as a new industrial product. It further relates to the method for preparing said composition and to its application in the protection of metallic surfaces, and in particular against corrosion caused by water in liquid or steam form.
- Such conditionings may be done with many mineral substances such as phosphates, polyphosphates, chromates, silicates, nitrites, sulfites, etc., or with organic ones, such as thiols, thiazols, amines, tannins, etc.; and selected as a function of the characteristics of the water used and of the installations proper.
- mineral substances such as phosphates, polyphosphates, chromates, silicates, nitrites, sulfites, etc.
- organic ones such as thiols, thiazols, amines, tannins, etc.
- amines phosphorous derivatives are found for example amines phosphorous derivatives, as well as amines proper.
- phosphorous derivatives recommended as anti-corrosion agents are aminophosphonic acids and their water-soluble salts described in French Pat. Nos. 1,430,798, 1,453,022, 1,461,087, and 1,474,068 and in published French Applications Nos. 2,060,416, 2,144,900, 2,148,260, 2,174,091, 2,184,939, 2,184,940 and 2,259,105.
- the said documents give the specific conditions in which the said aminophosphonic acids should be stoichiometrically neutralized with mineral or organic bases, and should be associated with salts that are soluble in water containing polyvalent metallic cations, such as certain zinc or chromium salts, and associated with certain organic inhibitors containing sulphur. It should however be noted that the aminophosphonic acids described previously are still presented and used in the form of water-soluble compounds to produce effects reducing the corrosion of metals to a loss of thickness always greater than or equal to 100 ⁇ /ann., at a dose of 5 ppm, and particularly with ferrous metals.
- amines have also been proposed as anti-corrosion agents, which have a molecular weight less than 300; these are ammonia, hydrazine, alkylamines (and in particular in C 1 -C 4 ), morpholine, benzylamine, cyclohexylamine, alkanolamines (see for example published French Patent Application No. 2,310,420) and polyalkylenepolyamines (see for example U.S. Pat. Nos. 3,069,225 and 2,857,333 and Dutch Pat. No.
- fatty alkylamines in C 12 -C 22 have been recommended and in particular that of dehydroabietylamine, larylamine, and stearylamine and their acid addition salts with HCl and CH 3 COOH, as well as of aliphatic polyamines with long chains known as "fatty polyamines" (see French Pat. No. 1,435,023), such as stearylaminopropyleneamine.
- fatty polyamines see French Pat. No. 1,435,023
- the disadvantage with these fatty alkylamines and polyamines is that they give an inadequate inhibition against corrosion produced by water, since the loss of thickness of the metallic surfaces (and particularly Fe or Cu surfaces) is of the order of 80 to 100 ⁇ /ann. in the best conditions of use.
- the inhibitors of the prior art and their salts lead at the most to a loss of thickness of between 80 and 150 ⁇ /ann.
- Another object of the invention is to propose a new anti-corrosion composition with an anti-corrosion power greater than that of the means recommended before. Indeed, in a large number of cases, the rates of residual corrosion through water (loss of thickness between 80 and 150 ⁇ /ann.) are still judged to be too high considering the repair and maintenance costs of the installations and considering the production or operation stoppages often necessitated by such repairs or by replacements. For example, compared with the solution proposed in published French Patent Application No.
- the present invention proposes a new anti-corrosion composition containing at least a polyamine and at least an alkylenephosphonic acid derivative, with which composition it is possible to reach, for metal surfaces needing to be protected from water for example, losses of thickness below, or equal to 50 ⁇ /ann.
- aminoalkylenephosphonic acid derivatives are meant here acids, salts and esters with, in their molecule, at least a fragment ##STR1## (wherein the alkylene group has a straight or branched hydrocarbon chain, and the dotted lines are bonds with other groups) as indicated in French Pat. No. 1,430,798.
- alkylenepolyphosphonic acid derivative is meant here a compound with at least two phosphonic functions and which is particularly selected from the group constituted by the alkylenepolyphosphonic acids, their esters and their mineral salts (such as for example metallic salts and NH 4 + ), the alkylene chain containing no amino group.
- the anti-corrosion composition according to the invention which comprises at least a polyamine and at least an alkylene-phosphonic acid derivative is a water-insoluble composition containing;
- R is a saturated or unsaturated aliphatic C 12 -C 22 hydrocarbon radical; and n 1 is an integer varying between 1 and 7 inclusive, R and n 1 being such that the molecular weight of the said polyamine is greater than or equal to 320; and
- suitable polyamines of formula I can be mentioned dodecyltri(aminopropylene)amine, dodecyltetra(aminopropylene)amine, hexadecyltri(aminopropylene)amine, hexadecenyltetra(aminopropylene)amine, octadecylaminopropyleneamine, octadecylpenta(aminopropylene)amine, octadecenyltetra(aminopropylene)amine, octadecyltri(aminopropylene)amine, octadecenylhexa(aminopropylene)amine, and hexadecylhepta(aminopropylene)amine.
- the amines of formula I may be used such as they are found in the trade, either on their own or mixed together, in their pure or technical form. It is also possible to use polyamines prepared from fatty acids of animal or vegetable origin or polyamines of synthesis. Amongst suitable polyamines, found on the market are the products known under the trademarks DIOMEEN, DINORAM, TRINORAM, POLYRAM, LILAMIN and CEMULCAT, which contain at least a polyamine I, with a molecular weight greater than or equal to 320.
- Alk is an alkylene group in C 1 -C 6 with a straight or branched hydrocarbon chain
- n 2 is an integer varying between 1 and 6 inclusive;
- Z 1 is H or an alkyl group in C 1 -C 5 ;
- Z 2 is an alkylene group in C 2 -C 5 ;
- Z 3 is an alkylene group in C 3 -C 5 ;
- n 3 is an integer varying between 1 and 20 inclusive, and
- n 4 is an integer varying between 1 and 4.
- acids of formula II the following can be mentioned by way of example and non-restrictively: aminotri(methylphosphonic)acid, aminotri(ethylphosphonic)acid, aminotri(butylphosphonic)acid, aminotri[( ⁇ , ⁇ -dimethyl)methylphosphonic]acid.
- acids of formula V the following can be cited by way of example and non-restrictively, diethoxypropylaminodi(methylphosphonic)acid, undecaethoxypropylaminodi(ethylphosphonic)acid and pentapropoxypropylaminodi(methylphosphonic)acid.
- A is a bivalent alkylene group comprising a straight and saturated C 1 -C 10 hydrocarbon chain, each carbon atom of which chain can be, if necessary, substituted by at least a group selected from the OH, C 1 -C 4 -alkyl and phosphonic groups ##STR4## and M 1 , M 2 , M 3 , M 4 , M 5 and M 6 , whether identical or different are each H, an alkyl group in C 1 -C 4 , NH 4 + or a metal cation.
- Suitable groups A are the --(CH 2 ) m [wherein m is an integer with a value varying between 1 and 10], ##STR5## wherein p is an integer with a value varying between 0 and 8.
- Other suitable groups A are given hereinafter.
- the preferred ones are the salts NH 4 + and salts of monovalent metals such as alkaline metals Na and K.
- alkylenepolyphosphonic acids (M 1 ⁇ M 2 ⁇ M 3 ⁇ M 4 ⁇ M 5 ⁇ M 6 ⁇ H), in particular alkylenediphosphonic, alkylenetriphosphonic and alkylenetetraphosphonic acids.
- Alkylenephosphonic acids answering to the aforesaid formulae II to VI may be chemically pure substances or technical products normally manufactured industrially and commercialized in liquid, paste or powder form, or even in aqueous solution form at any concentration, without the choice of one of these forms in any way constituting a restriction to the invention.
- the alkylenephosphonic acids commercialized in aqueous solution forms are preferred.
- composition according to the invention will contain (a) 5 to 80 parts by weight of polyamine I and (b) 20 to 95 parts by weight of the alkylenephosphonic acid derivative and, preferably (a) 15 to 70 parts by weight of polyamine I and (b) 30 to 85 parts by weight of derivative of the alkylenephosphonic acid of formulae II to VI.
- the method for preparing the anti-corrosion composition is performed in a manner known per se which consists in mixing one or more polyamines I with one or more derivatives of alkylenephosphonic acid.
- the method used is characterized in that the polyamine or polyamines selected is/are brought to a liquid state by adequate heating, and then introduced progressively whilst slightly or strongly stirred, depending on the case, in an aqueous solution of the alkylenephosphonic acid(s), selected, heated beforehand to a temperature less than that of the polyamine.
- the resulting mixture may be in gel, or paste or wax form.
- the polyamine(s) will be melted at a temperature varying between 30° and 85° C. approximately, and then poured into the alkylenephosphonic acid(s) brought to a temperature varying between 15° and 60° C.
- mixtures, with higher softening points will be preferred as anti-corrosion agents for metallic surfaces subjected to high temperatures, such as for example those found in steam boiler tubes or superheater tubes, or else those found in the cooling circuits of furnaces used in metallurgy and siderurgy.
- the paste or gel compositions, produced according to the invention can be introduced, by means of a conventional volumetric piston pump, either as they stand in the water of the industrial or private building systems requiring protection, or dispersed in a larger quantity of water using one or more surface active substances found on the market and known to any one skilled in the art as capable of dispersing fatty polyamines.
- the quantities of substances with surface-active properties used to this effect are dependent on the commercial aspect wanted for such dispersions and could not in any way constitute a restriction of the present invention.
- an anticorrosion composition according to the invention which composition can take the form of an aqueous bath, if necessary.
- non-ionic and/or cationic surface-active agents include those included preferably in the group of non-ionic and/or cationic surface-active agents.
- suitable non-ionic substances are ethoxylated or propoxylated fatty acids and alcohols, ethoxylated fatty monoamines, esters of fatty acids or alcohols, aliphatic amine oxides, sorbitol esters, etc.
- suitable, so-called cationic substances are amines salts, quaternary ammonium salts, products resulting from the condensation of ethylene oxide or propylene oxide with fatty polyamines.
- Stable dispersions in water may be obtained for example with industrial products selected from those known under the trademarks: NORAMOX, ETHOMEEN, DINORAMOX, ETHODUOMEEN, ETHOQUAD, ARQUAD, NORAMIUM, NOXAMINE, ADOGEN, ELFAPUR, AROMOX, etc.
- the resulting paste composition whose solubility is less than 1% by weight in distilled water, is an excellent anti-corrosion agent according to the invention, as will be seen hereinafter.
- the paste obtained after a return to room temperature appears, when thorougly examined, as a reverse dispersion of water in a yellow amber organic phase, which is found to have but a very low degree of solubility in water.
- Such composition is an excellent anti-corrosion agent as the experiments described hereinafter have proved.
- a homogeneous gel of yellow amber color is instantly obtained, which gel has a very small degree of solubility in water, but despite this fact, constitutes an excellent anti-corrosion agent for steel, copper, and aluminium in the presence of water.
- the circuit which is mainly made of glass, with a total capacity of 19.6 liters, and topped with an expansion vessel open at the top, also made of glass and with a contents capacity of 5 liters, is provided with an adjustable draining tap, that may be used discontinuously for heating tests and continuously for cooling tests.
- the flow rate of 1.6 m 3/hr is ensured by a centrifugal pump (for example one such as manufactured by the company HALBERG GmbH of Ludwigshafen, West Germany) and is controlled with a rotameter.
- the straight portions of the circuit are tubes of industrial glass, whose diameter is 40 mm and whose total length is 3 meters.
- the flowing speed of the water is about 1.5 meters per second.
- Said circuit further comprises means for controlling the efficiency of the inhibitors:
- a double probe connected to an electronic analyzer of the CORRATER type (commercialized by the company MAGNE INSTRUMENTS ROHRBACK CORP. of Santa Fe Springs, Ca.), provided with a recorder for potentio-static measurements of corrosion speed, and with a converter for alternatively measuring the so-called “generalized” corrosion and the corrosion known as "pitting".
- the specific electrodes of the potentio-static CORRATER analyzer have the references 60814-8001 for measurements effected on steel, 60814-8061 for measurements effected on copper, and 60814-8080 for measurements effected on aluminium.
- test pieces for measuring the weight losses are cylinder-shaped and hollow, 50 mm long, with an outer diameter of 21.3 to 22 mm, and an inner diameter of 14.8 to 17 mm, and with an external surface of 33.45 to 34.55 cm2, in contact with the attacking medium, and weighing in average 72.5 g for the steel pieces, 69 g for the copper pieces and 21.2 g for the aluminium pieces.
- the metal pieces are polished with a mild abrasive normally found on the market, washed in distilled water, dried in ketone and weighed with accuracy at ⁇ 1 ⁇ 10 -4 g. They are then mounted in series, three by three, each of a different metal, at a distance from one another and held together in position by an appropriate system in Teflon, and then introduced horizontally in a straight glass portion of the circuit. After the tests, they are removed from the circuit, brushed with a soft brush to remove all corrosion products, and washed in distilled water, dried in ketone and weighed very accurately at ⁇ 1 ⁇ 10 -4 g.
- the tests were carried out with four different varieties of water, namely tap water (tap water A1 for the anti-corrosion compositions of Examples 1-3, and tap water A2 for the anti-corrosion compositions of Examples 4-6) and soft water (soft water B1 for the anti-corrosion compositions of Examples 1-3, and soft water B2 for the anti-corrosion compositions of Examples 4-6), the soft waters B1 and B2, respectively, being obtained from the tap waters A1 and A2 respectively by passage over a ion-exchanging resin, of the cationic type in sodium cycle.
- tap water tap water A1 for the anti-corrosion compositions of Examples 1-3, and tap water A2 for the anti-corrosion compositions of Examples 4-6
- soft water soft water B1 for the anti-corrosion compositions of Examples 1-3, and soft water B2 for the anti-corrosion compositions of Examples 4-6
- Tap waters A1 and A2 (drinkable waters distributed by the city of PARIS) were used as they are for corrosion tests of the "cold” type and soft waters B1 and B2 were used for the corrosion tests of the "heat" type.
- d specific mass of the metal of the test piece given in g/cm3.
- Tables II to V relate to the measurements of weight losses, and Tables IV and V to the potentiostatic measurements for assessing the speeds of corrosion (expressed in microns per annum).
- control measurements i.e. measurements without inhibitor
- the measurements in the presence of the inhibitor where carried out for two months, for each composition tested and at two different dosages, within an approximate ratio of 10 to 1, depending on the mechanical possibilities of dispersion in the water of the compositions of Examples 1 to 6 above, without a surface-active agent having been used.
- the circuit has been modified by the introduction into its straight portion of a hollow steel probe, of 240 mm long and with an outside diameter of 28 mm, provided with a heating element which is adjustable by way of the rheostat.
- the metal test pieces for measuring the weight losses and the "CORRATER” probe are retained, as with the "HEAT" type tests.
- the circuit is filled and then supplied continuously with tap water from the city of PARIS, having the characteristics indicated in TABLE I and at the rate of about 20 liters per hour, entailing the renewing of the circuit water every hour in average.
- the drainage is controlled continuously so that the water level in the expansion vessel is kept constant.
- the anti-corrosion paste, according to the compositions of the invention is simply immersed in the expansion vessel by means of a linen bag.
- the temperature of the water, kept in forced circulation by the centrifugal pump and measured by a thermometer placed upstream of the heated probe, is stabilized at 50° C. ⁇ 5° C.
- Each test lasts 15 days with or without the inhibitors of Examples 1 to 6 above.
- the same measurements are carried out as for the "HEAT" type tests, with the only difference that at the end of the tests, the cylindrical test pieces in steel, copper and aluminium, as well as the heated probe made of steel, are washed before being brushed, with a diluted solution of passivated sulfamic acid, before removing any possible deposits of mineral salts that could be due to the hardness of the tap water and which the phosphonic acids, present in possibly insufficient quantities in the compositions according to the invention, could not have prevented.
- Tables VI to IX relate to the measurement of weight losses and Tables VIII and IX to potentiostatic measurements for assessing the speeds of corrosion.
- test pieces As well as the heated probe, appear to be coated with a very fine white powder which is removed easily with a soft brush, even from the heated probe.
- a rince in diluted sulfamic acid is nevertheless done as a precaution measure.
- a microscope examination shows that all the test pieces and the heated probe are completely pitting-free.
- the steel test-pieces are smooth, of a brownish color, more pronounced than on the heated probe.
- the copper and aluminium test pieces are a little less shiny than in the "HEAT" type tests.
- the other metallic elements of the circuit appear after dismantling, brushing and rincing in sulfamic acid, totally free of any deposits of corrosion and of any visible corroding.
- Examples 1 to 6 and Tables II to IX also show that important variations in the nature and respective proportions of the constituants of the compositions according to the invention have no significant effect on the anti-corrosion properties thereof. It is also a remarkable fact that the compositions according to the invention require no adjustment of the pH of the corrosive medium nor the addition of specific inhibitors, for copper for example. It is finally remarkable that in doses of 5 parts per one million, the compositions according to the invention show an anti-corrosion power that is clearly greater than the anti-corrosion powers of each of their constituents, taken separately, in substantially higher doses.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR7829312 | 1978-10-13 | ||
FR7829312A FR2453911A1 (fr) | 1978-10-13 | 1978-10-13 | Composition inhibitrice de corrosion, son procede de preparation et son application dans la protection des surfaces metalliques |
FR7916763 | 1979-06-28 | ||
FR7916763A FR2460338A2 (fr) | 1979-06-28 | 1979-06-28 | Composition inhibitrice de corrosion, son procede de preparation et son application dans la protection des surfaces metalliques |
Publications (1)
Publication Number | Publication Date |
---|---|
US4276089A true US4276089A (en) | 1981-06-30 |
Family
ID=26220801
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US06/083,553 Expired - Lifetime US4276089A (en) | 1978-10-13 | 1979-10-10 | Anticorrosion composition |
Country Status (7)
Country | Link |
---|---|
US (1) | US4276089A (fr) |
EP (1) | EP0010485B1 (fr) |
BR (1) | BR7906560A (fr) |
CA (1) | CA1122394A (fr) |
DD (1) | DD146629A5 (fr) |
DE (1) | DE2962827D1 (fr) |
OA (1) | OA06353A (fr) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4437898A (en) | 1980-08-27 | 1984-03-20 | Henkel Kommanditgesellschaft Auf Aktien | Method and agent for passivating iron and steel surfaces |
US4562042A (en) * | 1983-08-03 | 1985-12-31 | Societe Anonyme dite: Union Chimique et Industrielle de l'Quest (U.C.I.O.-S.A.) | Anticorrosive composition |
US4649025A (en) * | 1985-09-16 | 1987-03-10 | W. R. Grace & Co. | Anti-corrosion composition |
US4911887A (en) * | 1988-11-09 | 1990-03-27 | W. R. Grace & Co.-Conn. | Phosphonic acid compounds and the preparation and use thereof |
US4981648A (en) * | 1988-11-09 | 1991-01-01 | W. R. Grace & Co.-Conn. | Inhibiting corrosion in aqueous systems |
US4994195A (en) * | 1989-06-21 | 1991-02-19 | Edmondson James G | Inhibitor treatment program for chlorine dioxide corrosion |
US5017306A (en) * | 1988-11-09 | 1991-05-21 | W. R. Grace & Co.-Conn. | Corrosion inhibitor |
US5266722A (en) * | 1988-11-09 | 1993-11-30 | W. R. Grace & Co.-Conn. | Polyether bis-phosphonic acid compounds |
US9758877B2 (en) | 2013-03-01 | 2017-09-12 | General Electric Company | Compositions and methods for inhibiting corrosion in gas turbine air compressors |
EP3260576A1 (fr) | 2016-06-22 | 2017-12-27 | Kurita Water Industries Ltd. | Émulsions aqueuses huile dans l'eau d'amines organiques |
US10906828B2 (en) | 2015-02-11 | 2021-02-02 | Cytec Industries Inc. | Modified amines useful as scale inhibitors in wet process phosphoric acid production |
US11555274B2 (en) * | 2017-09-21 | 2023-01-17 | Kurita Water Industries Ltd. | Method for improving efficiency of steam heating, and papermaking method |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2771417A (en) * | 1952-04-30 | 1956-11-20 | Nat Aluminate Corp | Inhibition of corrosion in return steam condensate lines |
US2857333A (en) * | 1956-06-20 | 1958-10-21 | Universal Oil Prod Co | Corrosion inhibitors |
US3069225A (en) * | 1960-01-27 | 1962-12-18 | Gen Mills Inc | Method of inhibiting corrosion |
FR1435020A (fr) | 1965-02-16 | 1966-04-15 | Pechiney Saint Gobain | Procédé de chloration du polychlorure de vinyle |
US3505238A (en) * | 1965-03-29 | 1970-04-07 | Calgon C0Rp | Methods and compositions for inhibiting scale in saline water evaporators |
US3671448A (en) * | 1970-09-10 | 1972-06-20 | Monsanto Co | Methods of scale inhibition using substoichiometric amounts of amino alcohol and phosphonic acids |
US3723333A (en) * | 1968-05-11 | 1973-03-27 | Henkel & Cie Gmbh | Method for inhibiting corrosion and mineral deposits in water systems |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3523894A (en) * | 1966-07-18 | 1970-08-11 | Sun Oil Co | Corrosion inhibitors |
DE2520265C2 (de) * | 1975-05-07 | 1983-11-03 | Degussa Ag, 6000 Frankfurt | Mittel zur Verhinderung von Korrosionen in wässrigen Systemen |
US4209487A (en) * | 1975-06-02 | 1980-06-24 | Monsanto Company | Method for corrosion inhibition |
-
1979
- 1979-10-09 EP EP79400727A patent/EP0010485B1/fr not_active Expired
- 1979-10-09 DE DE7979400727T patent/DE2962827D1/de not_active Expired
- 1979-10-10 US US06/083,553 patent/US4276089A/en not_active Expired - Lifetime
- 1979-10-12 CA CA337,470A patent/CA1122394A/fr not_active Expired
- 1979-10-12 BR BR7906560A patent/BR7906560A/pt unknown
- 1979-10-13 OA OA56913A patent/OA06353A/fr unknown
- 1979-10-15 DD DD79216235A patent/DD146629A5/de unknown
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2771417A (en) * | 1952-04-30 | 1956-11-20 | Nat Aluminate Corp | Inhibition of corrosion in return steam condensate lines |
US2857333A (en) * | 1956-06-20 | 1958-10-21 | Universal Oil Prod Co | Corrosion inhibitors |
US3069225A (en) * | 1960-01-27 | 1962-12-18 | Gen Mills Inc | Method of inhibiting corrosion |
FR1435020A (fr) | 1965-02-16 | 1966-04-15 | Pechiney Saint Gobain | Procédé de chloration du polychlorure de vinyle |
US3505238A (en) * | 1965-03-29 | 1970-04-07 | Calgon C0Rp | Methods and compositions for inhibiting scale in saline water evaporators |
US3723333A (en) * | 1968-05-11 | 1973-03-27 | Henkel & Cie Gmbh | Method for inhibiting corrosion and mineral deposits in water systems |
US3671448A (en) * | 1970-09-10 | 1972-06-20 | Monsanto Co | Methods of scale inhibition using substoichiometric amounts of amino alcohol and phosphonic acids |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4437898A (en) | 1980-08-27 | 1984-03-20 | Henkel Kommanditgesellschaft Auf Aktien | Method and agent for passivating iron and steel surfaces |
US4562042A (en) * | 1983-08-03 | 1985-12-31 | Societe Anonyme dite: Union Chimique et Industrielle de l'Quest (U.C.I.O.-S.A.) | Anticorrosive composition |
US4649025A (en) * | 1985-09-16 | 1987-03-10 | W. R. Grace & Co. | Anti-corrosion composition |
US5017306A (en) * | 1988-11-09 | 1991-05-21 | W. R. Grace & Co.-Conn. | Corrosion inhibitor |
US4981648A (en) * | 1988-11-09 | 1991-01-01 | W. R. Grace & Co.-Conn. | Inhibiting corrosion in aqueous systems |
US4911887A (en) * | 1988-11-09 | 1990-03-27 | W. R. Grace & Co.-Conn. | Phosphonic acid compounds and the preparation and use thereof |
US5266722A (en) * | 1988-11-09 | 1993-11-30 | W. R. Grace & Co.-Conn. | Polyether bis-phosphonic acid compounds |
US5312953A (en) * | 1988-11-09 | 1994-05-17 | W. R. Grace & Co.-Conn. | Polyether bis-phosphonic acid compounds |
US4994195A (en) * | 1989-06-21 | 1991-02-19 | Edmondson James G | Inhibitor treatment program for chlorine dioxide corrosion |
US9758877B2 (en) | 2013-03-01 | 2017-09-12 | General Electric Company | Compositions and methods for inhibiting corrosion in gas turbine air compressors |
US10906828B2 (en) | 2015-02-11 | 2021-02-02 | Cytec Industries Inc. | Modified amines useful as scale inhibitors in wet process phosphoric acid production |
EP3260576A1 (fr) | 2016-06-22 | 2017-12-27 | Kurita Water Industries Ltd. | Émulsions aqueuses huile dans l'eau d'amines organiques |
US11555274B2 (en) * | 2017-09-21 | 2023-01-17 | Kurita Water Industries Ltd. | Method for improving efficiency of steam heating, and papermaking method |
Also Published As
Publication number | Publication date |
---|---|
EP0010485A1 (fr) | 1980-04-30 |
DE2962827D1 (en) | 1982-07-01 |
CA1122394A (fr) | 1982-04-27 |
EP0010485B1 (fr) | 1982-05-12 |
DD146629A5 (de) | 1981-02-18 |
OA06353A (fr) | 1981-06-30 |
BR7906560A (pt) | 1980-06-24 |
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